Metathesis catalyst and process for use thereof

ABSTRACT

This invention relates to a catalyst compound comprising a combination of a cyclic alkyl amino carbene ligand and a benzylidene both attached to a Group 8 metal, preferably ruthenium atom. 
     This invention also relates to a process to make linear alpha-olefins comprising contacting a feed material and an optional alkene (such as ethylene) with the catalyst described above, wherein the feed material is a triacylglyceride, fatty acid, fatty acid alkyl ester, and/or fatty acid ester, typically derived from seed oil (e.g., biodiesel).

PRIORITY CLAIM

This invention claims priority to and the benefit of U.S. Ser. No.61/259,514, filed Nov. 9, 2009.

STATEMENT OF RELATED APPLICATIONS

This invention is related to patent application U.S. Ser. No. 12/______,filed concurrently herewith (Attorney Docket No. 2009EM273/2) andclaiming priority to U.S. Ser. No. 61/259,521, filed Nov. 9, 2009.

FIELD OF THE INVENTION

This invention relates to metathesis catalyst compounds and processesfor the use thereof.

BACKGROUND OF THE INVENTION

The cross-metathesis of ethylene and internal olefin to producealpha-olefins is generally referred to as ethenolysis. OlefinsConversion Technology™, based upon the Phillips Triolefin Process, is anexample of an ethenolysis reaction converting ethylene and 2-butene intopropylene. These processes uses heterogeneous catalysts, such astungsten and rhenium oxides, which have not proven effective forinternal olefins containing functional groups such as cis-methyl oleate,a fatty acid methyl ester.

Methods for the production of polyalpha-olefins are typically multi-stepprocesses that often create unwanted by-products and waste of reactantsand energy. Full range linear alpha-olefins plants are petroleum-based,are inefficient and result in mixtures of oligomerization products thattypically yield Schulz-Flory distributions producing large quantities ofundesirable materials. In recent years there have been new technologiesimplemented to produce “on purpose” linear alpha-olefins such 1-hexeneand 1-octene through chromium-based selective ethylene trimerization ortetramerization catalysts. Alternatively, 1-octene has been produced viathe telomerization of butadiene and methanol. Similar strategies are notcurrently available for the production of 1-decene.

1-Decene is a co-product in the cross-metathesis of ethylene and methyloleate. Alkyl oleates are fatty acid esters that can be major componentsin biodiesel produced by the transesterification of alcohol andvegetable oils. Vegetable oils containing at least one site ofunsaturation include canola, soybean, palm, peanut, mustard, sunflower,tung, tall, perilla, grapeseed, rapeseed, linseed, safflower, pumpkincorn and many other oils extracted from plant seeds. Alkyl erucatessimilarly are fatty acid esters that can be major components inbiodiesel. Useful biodiesel compositions are those which typically havehigh concentrations of oleate and erucate esters. These fatty acidesters preferably have one site of unsaturation such thatcross-metathesis with ethylene yields 1-decene as a co-product.

Biodiesel is a fuel prepared from renewable sources, such as plant oilsor animal fats. To produce biodiesel, triacylglycerides (“TAG”), themajor compound in plant oils and animal fats, are converted to fattyacid alkyl esters (“FAAE,” i.e., biodiesel) and glycerol via reactionwith an alcohol in the presence of a base, acid, or enzyme catalyst.Biodiesel fuel can be used in diesel engines, either alone or in a blendwith petroleum-based diesel, or can be further modified to produce otherchemical products.

Cross-metathesis catalysts reported thus far for the ethenolysis ofmethyl oleate are typically ruthenium-based catalysts bearing phosphineor carbene ligands. Dow researchers in 2004 achieved catalysts turnoversof approximately 15,000 using the 1^(st) generation Grubb's catalyst,bis(tricyclohexylphosphine)benzylidene ruthenium(IV) dichloride,(Organometallics 2004, 23, 2027). Researchers at Materia, Inc. havereported turnover numbers up to 35,000 using a ruthenium catalystcontaining a cyclic alkyl amino carbene ligand, (WO 2008/010961). Theseturnovers were obtained with a catalyst reportedly too expensive forindustrial consideration due to high costs associated with the catalystsbeing derived from a low yielding synthesis (See Final Technical Reportentitled “Platform Chemicals from an Oilseed Biorefinery” grant numberDE-FG36-04G014016 awarded by the Department of Energy). In order toobtain an economically viable process for 1-decene production via thecross-metathesis of ethylene and biodiesel or vegetable oils, higheractivity catalysts must be discovered. Thus there is a need for higheractivity processes that produce desired products and co-products incommercially desirable ratios.

Likewise, there is a need to develop a means to provide linearalpha-olefins (particularly high yields of linear alpha-olefins) bymetathesis reactions, particularly reactions with good conversion,preferably under mild reaction conditions is a minimal number of steps.The instant invention's metathesis catalyst provides both a commerciallyeconomical and an “atom-economical” route to linear alpha-olefins.

Specifically, the instant inventors have found that the combination of acyclic alkyl amino carbene ligand attached to ruthenium with a chelatingbenzylidene ligand containing an electron withdrawing group yielded acatalyst that is both highly active and very selective towards theethenolysis of methyl oleate yielding 1-decene and methyl-9-decenoate.

SUMMARY OF THE INVENTION

This invention relates to a process comprising contacting a seed oil orderivative thereof (and optional alkene) with an olefin metathesiscatalyst under conditions which yield an alpha-olefin.

This invention relates to a process comprising contacting atriacylglyceride or derivative thereof (and optional alkene) with anolefin metathesis catalyst under conditions which yield an alpha-olefin.

The novel process of this invention employs a novel catalyst comprisingthe combination of a cyclic alkyl amino carbene ligand and a benzylideneligand containing an electron withdrawing substituent on the aromaticring of the benzylidene both attached to a Group 8 metal, preferablyruthenium atom.

This invention further relates to a metathesis catalyst is representedby the formula:

where:M is a Group 8 metal;X and X¹ are, independently, any anionic ligand, or X and X¹ may bejoined to form a dianionic group and may form single ring of up to 30non-hydrogen atoms or a multinuclear ring system of up to 30non-hydrogen atoms;

L is N, O, P, or S;

R is hydrogen or a C₁ to C₃₀ hydrocarbyl or substituted hydrocarbyl;R¹, R², R³, R⁴, R⁵, R⁶, R⁷, and R⁸ are, independently, hydrogen or a C₁to C₃₀ hydrocarbyl or substituted hydrocarbyl;each R⁹ and R¹³ are, independently, hydrogen or a C₁ to C₃₀ hydrocarbylor substituted hydrocarbyl;R¹⁰, R¹¹, R¹² are, independently, hydrogen or a C₁ to C₃₀ hydrocarbyl orsubstituted hydrocarbyl;each G, is, independently, hydrogen, halogen or C₁ to C₃₀ substituted orunsubstituted hydrocarbyl,where any two adjacent R groups may form a single ring of up to 8non-hydrogen atoms or a multinuclear ring system of up to 30non-hydrogen atoms.

DETAILED DESCRIPTION

This invention relates to a process comprising contacting a seed oil orderivative thereof (and optional alkene) with an olefin metathesiscatalyst under conditions which yield an alpha-olefin. Typically theseed oil is esterified or transesterified with an alcohol prior tocontacting with the olefin metathesis catalyst.

This invention relates to a process comprising contacting atriacylglyceride or a derivative thereof with an optional alkene (suchas ethylene) and an olefin metathesis catalyst under conditions whichyield an alpha-olefin, typically yielding a linear alpha-olefin (such as1-decene, 1-heptene, and/or 1-butene) and an ester or acidfunctionalized olefin.

This invention further relates to a process for producing alpha-olefins(preferably linear alpha-olefins) comprising contacting atriacylglyceride with an alcohol (such as methanol) to produce a fattyacid alkyl ester and thereafter contacting the fatty acid alkyl esterwith an olefin metathesis catalyst (and optional alkene, such asethylene) under conditions which yield an alpha-olefin (preferably alinear alpha-olefin, preferably 1-decene, 1-heptene, and/or 1-butene)and an ester or acid functionalized olefin.

This invention further relates to a process for producing alpha-olefins(preferably linear alpha-olefins) comprising contacting atriacylglyceride with water and or an alkaline reactant (such as sodiumhydroxide) to produce a fatty acid and thereafter contacting the fattyacid with an olefin metathesis catalyst (and optional alkene, such asethylene) under conditions which yield an alpha-olefin (preferably alinear alpha-olefin, preferably 1-decene, 1-heptene, and/or 1-butene)and an ester or acid functionalized olefin.

This invention further relates to contacting unsaturated fatty acid withan alkene (such as ethylene) in the presence of an olefin metathesiscatalyst under conditions which yield an alpha-olefin (preferably alinear alpha-olefin, preferably 1-decene, 1-heptene, and/or 1-butene)and an ester or acid functionalized olefin.

This invention further relates to contacting an unsaturated fatty acidester with a alkene (such as ethylene) in the presence of an olefinmetathesis catalyst under conditions which yield an alpha-olefin(preferably a linear alpha-olefin, preferably 1-decene, 1-heptene,and/or 1-butene) and an ester or acid functionalized olefin.

This invention further relates to contacting an unsaturated fatty acidalkyl ester with a alkene (such as ethylene) in the presence of anolefin metathesis catalyst under conditions which yield an alpha-olefin(preferably a linear alpha-olefin, preferably 1-decene, 1-heptene,and/or 1-butene) and an ester or acid functionalized olefin.

This invention also relates to a process to produce alpha olefin(preferably linear alpha olefin, preferably 1-decene, 1-heptene and or1-butene) comprising contacting a metathesis catalyst with an alkene(preferably ethylene), and one or more fatty acid esters (preferablyfatty acid methyl esters, preferably methyl oleate).

In a preferred embodiment, this relates to a process to produce alphaolefin (preferably linear alpha olefin, preferably 1-decene, 1-hepteneand or 1-butene) comprising contacting a metathesis catalyst with analkene (preferably ethylene), and one or more fatty acid esters(preferably fatty acid methyl esters, preferably methyl oleate) derivedfrom biodiesel.

In a preferred embodiment, the olefin metathesis catalysts describedherein may be combined directly with triacylglycerides, biodiesel, fattyacids, fatty acid esters and/or fatty acid alkyl esters to producealpha-olefins, preferably linear alpha olefins, preferably C₄ to C₂₄alpha-olefins, preferably linear alpha-olefins, such as 1-decene,1-heptene and or 1-butene.

In a preferred embodiment, a mixture of one or more triacylglyceride,biodiesel, fatty acids, fatty acid esters and/or fatty acid alkyl estersare used to produce alpha-olefins, preferably linear alpha olefins,preferably C₄ to C₂₄ alpha-olefins, preferably C₄ to C₂₄ linearalpha-olefins. In a preferred embodiment a mixture of alpha olefins,preferably linear alpha olefins, preferably 1-decene, 1-heptene and or1-butene are produced.

Process

In a preferred embodiment, the metathesis catalysts described herein maybe combined directly with seed oils, triacylglyceride, biodiesel, fattyacids, fatty acid esters and/or fatty acid alkyl esters (“feedmaterials”) to produce alpha-olefins, preferably linear alpha olefins,preferably C₄ to C₂₄ alpha-olefins, preferably C₄ to C₂₄ linearalpha-olefins, such as preferably 1-decene, 1-heptene and or 1-butene.

Typically, the molar ratio of alkene to unsaturated feed material (suchas unsaturated fatty acid or fatty acid ester) is greater than about0.8/1.0, preferably, greater than about 0.9/1.0. Typically, the molarratio of alkene to feed material (such as unsaturated fatty acid orfatty acid ester) is less than about 3.0/1.0, preferably, less thanabout 2.0/1.0. Depending upon the specific reagents, other molar ratiosmay also be suitable. With ethylene, for example, a significantly highermolar ratio can be used, because the self-metathesis of ethyleneproduces only ethylene again; no undesirable co-product olefins areformed. Accordingly, the molar ratio of ethylene to feed material (suchas unsaturated fatty acid or fatty acid ester) may range from greaterthan about 0.8/1 to typically less than about 20/1.

The quantity of metathesis catalyst that is employed in the process ofthis invention is any quantity that provides for an operable metathesisreaction. Preferably, the ratio of moles of feed material (preferablyfatty acid ester and or fatty acid alkyl ester) to moles of metathesiscatalyst is typically greater than about 10:1, preferably, greater thanabout 100:1, preferably greater than about 1000:1, preferably greaterthan about 10,000:1, preferably greater than about 25,000:1, preferablygreater than about 50,000:1, preferably greater than about 100,000:1.Alternately, the molar ratio of feed material (preferably fatty acidester and or fatty acid alkyl ester) to metathesis catalyst is typicallyless than about 10,000,000:1, preferably, less than about 1,000,000:1,and more preferably, less than about 500,000:1.

The contacting time of the reagents and catalyst in a batch reactor canbe any duration, provided that the desired olefin metathesis productsare obtained. Generally, the contacting time in a reactor is greaterthan about 5 minutes, and preferably, greater than about 10 minutes.Generally, the contacting time in a reactor is less than about 25 hours,preferably, less than about 15 hours, and more preferably, less thanabout 10 hours.

In a preferred embodiment, the reactants (for example, metathesiscatalyst; feed materials; optional alkene, optional alcohol, optionalwater, etc) are combined in a reaction vessel at a temperature of 20 to200° C. (preferably 30 to 100° C., preferably 40 to 60° C.) and analkene (such as ethylene) pressure of 0.1 to 1000 psi (preferably 20 to400 psi, preferably 50 to 250 psi), if the alkene is present, for aresidence time of 0.5 seconds to 48 hours (preferably 0.25 to 5 hours,preferably 30 minutes to 2 hours).

In a preferred embodiment, from about 0.005 nmoles to about 500 nmoles,preferably from about 0.1 to about 250 nmoles, and most preferably fromabout 1 to about 50 nmoles of the metathesis catalyst are charged to thereactor per 3 mmoles of feed material (such as TAGs, biodiesel, fattyacids, fatty acid esters and/or fatty acid alkyl esters or mixturesthereof, preferably fatty acid esters) charged.

In a preferred embodiment, the alkane and an unsaturated fatty acidester or unsaturated fatty acid are co-metathesized to form first andsecond product olefins, preferably, a reduced chain first productalpha-olefin and a second product reduced chain terminal ester oracid-functionalized alpha-olefin. As a preferred example, the metathesisof methyloleate with ethylene will yield co-metathesis products of1-decene and methyl-9-decenoate. Both products are alpha-olefins; thedecenoate also terminates in an ester moiety at the opposite end of thechain from the carbon-carbon double bond. In addition to the desiredproducts, the methyloleate may self-metathesize to produce small amountsof 9-octadecene, a less desirable product, and dimethyloctadec-9-enoate,CH₃O(O)C(CH₂)₇CH═CH(CH₂)₇C(O)OCH₃, a second less desirable product.

In the process of this invention, the conversion of feed material(preferably fatty acid ester and or fatty acid alkyl ester) can varywidely depending upon the specific reagent olefins, the specificcatalyst, and specific process conditions employed. For the purpose ofthis invention, “conversion” is defined as the mole percentage of feedmaterial that is converted or reacted to products. Typically, theconversion of feed material (preferably fatty acid ester and or fattyacid alkyl ester) is greater than about 50 mole percent, preferably,greater than about 60 mole percent, and more preferably, greater thanabout 70 mole percent.

In the process of this invention, the yields of first product olefin andester or acid-functionalized second product olefin can also varydepending upon the specific reagent olefins, catalyst, and processconditions employed. For the purposes of this invention “yield” will bedefined as the mole percentage of product olefin formed relative to theinitial moles of feed material (such as fatty acid ester and or fattyacid alkyl ester) in the feed. Typically, the yield of alpha-olefin willbe greater than about 35 mole percent, preferably, greater than about 50mole percent. Typically, the yield of ester or acid-functionalizedalpha-olefin will be greater than about 35 mole percent, preferably,greater than about 50 mole percent.

In a preferred embodiment, the process is typically a solution process,although it may be a bulk or high pressure process. Homogeneousprocesses are preferred. (A homogeneous process is defined to be aprocess where at least 90 wt % of the product is soluble in the reactionmedia.) A bulk homogeneous process is particularly preferred. (A bulkprocess is defined to be a process where reactant concentration in allfeeds to the reactor is 70 volume % or more.) Alternately no solvent ordiluent is present or added in the reaction medium, (except for thesmall amounts used as the carrier for the catalyst or other additives,or amounts typically found with the reactants; e.g., propane inpropylene).

Suitable diluents/solvents for the process include non-coordinating,inert liquids. Examples include straight and branched-chain hydrocarbonssuch as isobutane, butane, pentane, isopentane, hexanes, isohexane,heptane, octane, dodecane, and mixtures thereof; cyclic and alicyclichydrocarbons such as cyclohexane, cycloheptane, methylcyclohexane,methylcycloheptane, and mixtures thereof such as can be foundcommercially (Isopar™); perhalogenated hydrocarbons such asperfluorinated C₄₋₁₀ alkanes, chlorobenzene, and aromatic andalkylsubstituted aromatic compounds such as benzene, toluene,mesitylene, and xylene. Suitable diluents/solvents also include aromatichydrocarbons, such as toluene or xylenes, and chlorinated solvents, suchas dichloromethane. In a preferred embodiment, the feed concentrationfor the process is 60 volume % solvent or less, preferably 40 volume %or less, preferably 20 volume % or less.

The process may be batch, semi-batch or continuous. As used herein, theterm continuous means a system that operates without interruption orcessation. For example, a continuous process to produce a polymer wouldbe one where the reactants are continually introduced into one or morereactors and polymer product is continually withdrawn.

Useful reaction vessels include reactors (including continuous stirredtank reactors, batch reactors, reactive extruder, pipe or pump.

If the process is conducted in a continuous flow reactor, then theweight hourly space velocity, given in units of grams feed material(preferably fatty acid ester and or fatty acid alkyl ester) per gramcatalyst per hour (h⁻¹), will determine the relative quantities of feedmaterial to catalyst employed, as well as the residence time in thereactor of the unsaturated starting compound. In a flow reactor, theweight hourly space velocity of the unsaturated feed material(preferably fatty acid ester and or fatty acid alkyl ester) is typicallygreater than about 0.04 g feed material (preferably fatty acid ester andor fatty acid alkyl ester) per g catalyst per hour (h⁻¹), andpreferably, greater than about 0.1 h⁻¹. In a flow reactor, the weighthourly space velocity of the feed material (preferably fatty acid esterand or fatty acid alkyl ester) is typically less than about 100 h⁻¹, andpreferably, less than about 20 h⁻¹.

In a preferred embodiment, the productivity of the process is at least200 g of linear alpha-olefin (such as decene-1) per mmol of catalyst perhour, preferably at least 5000 g/mmol/hour, preferably at least 10,000g/mmol/hr, preferably at least 300,000 g/mmol/hr.

In a preferred embodiment, the selectivity of the process is at least 20wt % linear alpha-olefin, based upon the weight to the material exitingthe reactor, preferably at least 25%, preferably at least 30%,preferably at least 35%.

In a preferred embodiment, the turnover number (TON), defined as themoles of alpha olefin formed per mol of catalyst, of the process is atleast 10,000, preferably at least 50,000, preferably at least 100,000,preferably at least 1,000,000.

In a preferred embodiment, the yield (when converting unsaturated fattyacids, unsaturated fatty acid esters, unsaturated fatty acid alkylesters or mixtures thereof), defined as the moles of alpha olefin formedper mol of unsaturated fatty acids, unsaturated fatty acid esters,unsaturated fatty acid alkyl esters or mixtures thereof introduced intothe reactor, is 30% or more, preferably 40% or more, preferably 45% ormore, preferably 50% or more, preferably 55% or more, preferably 60% ormore.

In a preferred embodiment, the yield for reactions (when converting TAGsas represented in the formula below), is defined as the moles of alphaolefin formed divided by (the moles of unsaturated R^(a)+moles ofunsaturated R^(b)+moles of unsaturated R^(c)) introduced into thereactor is 30% or more, preferably 40% or more, preferably 45% or more,preferably 50% or more, preferably 55% or more, preferably 60% or more.

where R^(a), R^(b) and R^(c) each, independently, represent a saturatedor unsaturated hydrocarbon chain (preferably R^(a), R^(b) and R^(c)each, independently, are a C₁₂ to C₂₈ alkyl or alkene, preferably C₁₆ toC₂₂ alkyl or alkene).

Alkenes

Besides the feed materials, the metathesis process of this invention mayrequire a an alkene as a reactant. The term “alkene” shall imply anorganic compound containing at least one carbon-carbon double bond andtypically having less than about 10 carbon atoms. The alkene may haveone carbon-carbon unsaturated bond, or alternatively, two or morecarbon-carbon unsaturated bonds. Since the metathesis reaction can occurat any double bond, alkenes having more than one double bond willproduce more metathesis products. Accordingly, in some embodiments, itis preferred to employ an alkene having only one carbon-carbon doublebond. The double bond may be, without limitation, a terminal double bondor an internal double bond. The alkene may also be substituted at anyposition along the carbon chain with one or more substituents, providedthat the one or more substituents are essentially inert with respect tothe metathesis process. Suitable substituents include, withoutlimitation, alkyl, preferably, C₁₋₆ alkyl; cycloalkyl, preferably, C₃₋₆cycloalkyl; as well as hydroxy, ether, keto, aldehyde, and halogenfunctionalities. Non-limiting examples of suitable alkenes includeethylene, propylene, butene, butadiene, pentene, hexene, the variousisomers thereof, as well as higher homologues thereof. Preferably, thealkene is a C₂₋₈ alkene. More preferably, the alkene is a C₂₋₆ alkene,even more preferably, a C₂₋₄ alkene, and most preferably, ethylene.

Useful alkenes include those represented by the formula: R*—HC═CH—R*,wherein each R* is independently, hydrogen or a C₁ to C₂₀ hydrocarbyl,preferably hydrogen or a C₁ to C₆ hydrocarbyl, preferably hydrogen,methyl, ethyl, propyl or butyl, more preferably R* is hydrogen. In apreferred embodiment, both R* are the same, preferably both R*arehydrogen. Ethylene, propylene, butene, pentene, hexene, octene andnonene (preferably ethylene) are alkenes useful herein.

For purposes of this invention and the claims thereto, the term lowerolefin means an alkene represented by the formula: R*—HC═CH—R*, whereineach R* is independently, hydrogen or a C₁ to C₆ hydrocarbyl, preferablyhydrogen or a C₁ to C₃ hydrocarbyl, preferably hydrogen, methyl, ethyl,propyl or butyl, more preferably R* is hydrogen. In a preferredembodiment, both R* are the same, preferably both R*are hydrogen.Ethylene, propylene, butene, pentene, hexene, and octene (preferablyethylene) are lower olefins useful herein.

Triacylgycerides

Triacylglycerides (TAGs), also called triglycerides, are a naturallyoccurring ester of three fatty acids and glycerol that is the chiefconstituent of natural fats and oils. The three fatty acids can be alldifferent, all the same, or only two the same, they can be saturated orunsaturated fatty acids, and the saturated fatty acids may have one ormultiple unsaturations. Chain lengths of the fatty acids in naturallyoccurring triacylglycerides can be of varying lengths but 16, 18 and 20carbons are the most common. Natural fatty acids found in plants andanimals are typically composed only of even numbers of carbon atoms dueto the way they are bio-synthesized. Most natural fats contain a complexmixture of individual triglycerides and because of this, they melt overa broad range of temperatures.

Biodiesel is a mono-alkyl ester derived from the processing of vegetableoils and alcohols. The processing is typically carried out by anesterification reaction mechanism, and typically is performed in anexcess of alcohol to maximize conversion. Esterification can refer todirect esterification, such as between a free fatty acid and an alcohol,as well as transesterification, such as between an ester and an alcohol.While vegetable oil and alcohols are commonly employed as reactants inesterification reactions, a fatty acid source such as free fatty acids,soaps, esters, glycerides (mono-, di- tri-), phospholipids,lysophospholipids, or amides and a monohydric alcohol source, such as analcohol or an ester, can be esterified. In addition, variouscombinations of these reagents can be employed in an esterificationreaction.

Vegetable oils include triglycerides and neutral fats, such astriacylglyderides, the main energy storage form of fat in animals andplants. These typically have the chemical structure:

where R^(a), R^(b) and R^(c) each, independently, represent a saturatedor non-saturated hydrocarbon chain (preferably R^(a), R^(b) and R^(c)each, independently, are a C₁₂ to C₂₈ alkyl or alkene, preferably C₁₆ toC₂₂ alkyl or alkene). Different vegetable oils have different fatty acidprofiles, with the same or different fatty acids occurring on a singleglycerol. For example, an oil can have linoleic, oleic, and stearicacids attached to the same glycerol, with each of R^(a), R^(b) and R^(c)representing one of these three fatty acids. In another example, therecan be two oleic acids and one stearic acid attached to the sameglycerol, each of R^(a), R^(b) and R^(c) representing one of these fattyacids. A particularly useful triglyceride consists of three fatty acids(e.g., saturated fatty acids of general structure of CH₃(CH₂)_(n)COOH,wherein n is typically an integer of from 4 to 28 or higher) attached toa glycerol (C₃H₅(OH)₃) backbone by ester linkages. In the esterificationprocess, vegetable oils and short chain alcohols are reacted to formmono-alkyl esters of the fatty acid and glycerol (also referred to asglycerin). When the alcohol used is methanol (CH₃OH), a methyl ester iscreated with the general form CH₃(CH₂)_(n)COOCH₃ for saturated fattyacids. Typically, but not always, the length of the carbon backbonechain is from 12 to 24 carbon atoms.

The esterification process can be catalyzed or non-catalyzed. Catalyzedprocesses are categorized into chemical and enzyme based processes.Chemical catalytic methods can employ acid and/or base catalystmechanisms. The catalysts can be homogeneous and/or heterogeneouscatalysts. Homogeneous catalysts are typically liquid phase mixtures,whereas heterogeneous catalysts are solid phase catalysts mixed with theliquid phase reactants, oils and alcohols.

The fatty acid rich material useful in the processes described hereincan be derived from plant, animal, microbial, or other sources (feedoil). Preferred feed oils include vegetable oils such as corn, soy,rapeseed, canola, sunflower, palm and other oils that are readilyavailable; however, any vegetable oil or animal fat can be employed. Rawor unrefined oil can be used in certain embodiments; however, filteredand refined oils are typically preferred. Use of degummed and filteredfeedstock minimizes the potential for emulsification and blockage in thereactors. Feedstock with high water content can be dried before basiccatalyst processing. Feedstock with high free fatty acid content can bepassed through an esterification process to reduce the free fatty acidcontent before the process of esterification to convert fatty acidglycerides to monoalkyl esters. The reduction of free fatty acids andthe conversion of fatty acid glycerides can also in the same processingstep. Feedstock containing other organic compounds (such as hexane,heptane, isohexane, etc.) can typically be processed without significantmodifications to the reactor. Other materials containing fatty acidglycerides or other fatty acid esters can also be employed, includingphospholipids, lysophospholipids, and fatty acid wax esters. The fattyacid rich material useful in the processes described herein typicallyincludes a mixture of fatty acids. For example, the fatty acid profilesof several potential feedstocks are shown in Table 1. The feed oil canalso include a mixture of fatty acid glycerides from different sources.The free fatty acid content of useful vegetable oils is preferably about0.1 wt % or less when employed in a basic homogeneous catalystesterification reaction. Higher levels can be utilized as well, andlevels up to about 3 wt %, or even as high as 15 wt % or more cantypically be tolerated.

TABLE 1 Fatty Acid Profile of Several Typical Feed Oils Hi Oleic FattyAcid Palm Oil Soy Oil Rapeseed Yellow Grease 0 wt % 0 wt % 0 wt % 0 wt %C6:0 0 wt % 0 wt % 0 wt % 0 wt % C8:0 0 wt % 0 wt % 0 wt % 0 wt % C10:00 wt % 0 wt % 0 wt % 0 wt % C12:0 0 wt % 0 wt % 0 wt % 0 wt % C14:0 1 wt% 0 wt % 0 wt % 2 wt % C16:0 44 wt %  7 wt % 4 wt % 23 wt %  C18:0 5 wt% 5 wt % 1 wt % 13 wt %  C18:1 39 wt %  28 wt %  60 wt %  44 wt %  C18:210 wt %  53 wt %  21 wt %  7 wt % C18:3 0 wt % 0 wt % 13 wt %  1 wt %C20:0 0 wt % 0 wt % 0 wt % 0 wt % C22:1 0 wt % 0 wt % 0 wt % 0 wt %Misc. 1 wt % 8 wt % 0 wt % 9 wt % Total 100 wt %  100 wt %  100 wt % 100 wt % Alcohol (also Referred to as Alkanols)

The alcohol used herein can be any monohydric, dihydric, or polyhydricalcohol that is capable of condensing with the feed material (such asthe unsaturated fatty acid) to form the corresponding unsaturated ester(such as the fatty acid ester). Typically, the alcohol contains at leastone carbon atom. Typically, the alcohol contains less than about 20carbon atoms, preferably, less than about 12 carbon atoms, and morepreferably, less than about 8 carbon atoms. The carbon atoms may bearranged in a straight-chain or branched structure, and may besubstituted with a variety of substituents, such as those previouslydisclosed hereinabove in connection with the fatty acid, including theaforementioned alkyl, cycloalkyl, monocyclic aromatic, arylalkyl,alkylaryl, hydroxyl, halogen, ether, ester, aldehyde and ketosubstituents. Preferably, the alcohol is a straight-chain or branchedC₁₋₁₂ alkanol. A preferred alcohol is the trihydric alcohol glycerol,the fatty acid esters of which are known as “glycerides.” Otherpreferred alcohols include methanol and ethanol.

Preferably, the alcohol employed in the esterification and/ortransesterification reactions is preferably a low molecular weightmonohydric alcohol such as methanol, ethanol, 1-propanol, 2-propanol,1-butanol, 2-butanol, or t-butanol. The alcohol is preferably anhydrous;however, a small amount of water in the alcohol may be present (e.g.,less than about 2 wt %, preferably less than about 1 wt %, and mostpreferably less than about 0.5 wt %; however in certain embodimentshigher amounts can be tolerated). Acid esterification reactions are moretolerant of the presence of small amounts of water in the alcohol thanare basic transesterification reactions. While specific monohydricalcohols are discussed herein with reference to certain embodiments andexamples, the preferred embodiments are not limited to such specificmonohydric alcohols. Other suitable monohydric alcohols can also beemployed in the preferred embodiments.

Transesterification/Esterification Reactions

The conversion of TAGs to fatty acid alkyl esters (“FAAE”) throughtransesterification of the TAG typically involves forming a reactantstream, which includes TAG (e.g., at least about 75 wt %), alkanol(e.g., about 5 to 20 wt %), a transesterification catalyst (e.g., about0.05 to 1 wt %), and optionally, glycerol (typically up to about 10 wt%). Suitable alkanols may include C₁-C₆ alkanols and commonly mayinclude methanol, ethanol, or mixtures thereof. Suitabletransesterification catalysts may include alkali metal alkoxides havingfrom 1 to 6 carbon atoms and commonly may include alkali metalmethoxide, such as sodium methoxide and/or potassium methoxide. Thebasic catalyst is desirably selected such that the alkali metal alkoxidemay suitably contain an alkoxide group which is the counterpart of thealkanol employed in the reaction stream (e.g., a combination of methanoland an alkali metal methoxide such as sodium methoxide and/or potassiummethoxide). The reactant stream may suitably include about 0.05 to 0.3wt % sodium methoxide, at least about 75 wt % triacylglyceride, about 1to 7 wt % glycerol, and at least about 10 wt % methanol. In someembodiments, the reactant stream may desirably include about 0.05 to0.25 wt % sodium methoxide, at least about 75 wt % triacylglyceride,about 2 to 5 wt % glycerol, and about 10 to 15 wt % methanol.

The rate and extent of reaction for esterification of the fatty acidglycerides or other fatty acid derivates with monohydric alcohol in thepresence of a catalyst depends upon factors including but not limited tothe concentration of the reagents, the concentration and type ofcatalyst, and the temperature and pressure conditions, and time ofreaction. The reaction generally proceeds at temperatures above about50° C., preferably at temperatures above 65° C.; however, the catalystselected or the amount of catalyst employed can affect this temperatureto some extent. Higher temperatures generally result in faster reactionrates. However, the use of very high temperatures, such as those inexcess of about 300° C., or even those in excess of 250° C., can lead toincreased generation of side products, which can be undesirable as theirpresence can increase downstream purification costs. Higher temperaturescan be advantageously employed, however, e.g., in situations where theside products do not present an issue.

The reaction temperature can be achieved by preheating one or more ofthe feed materials or by heating a mixture of the feed materials.Heating can be achieved using apparatus known in the art e.g., heatexchangers, jacketed vessels, submerged coils, and the like. Whilespecific temperatures and methods of obtaining the specific temperaturesare discussed herein with reference to certain embodiments and examples,the preferred embodiments are not limited to such specific temperaturesand methods of obtaining the specific temperatures. Other temperaturesand methods of obtaining temperatures can also be employed in thepreferred embodiments.

The amount of alcohol employed in the reaction is preferably in excessof the amount of fatty acid present on a molar basis. The fatty acid canbe free or combined, such as to alcohol, glycol or glycerol, with up tothree fatty acid moieties being attached to a glycerol. Additionalamounts of alcohol above stoichiometric provide the advantage ofassisting in driving the equilibrium of the reaction to produce more ofthe fatty acid ester product. However, greater excesses of alcohol canresult in greater processing costs and larger capital investment for thelarger volumes of reagents employed in the process, as well as greaterenergy costs associated with recovering, purifying, and recycling thisexcess alcohol. Accordingly, it is generally preferred to employ anamount of alcohol yielding a molar ratio of alcohol to fatty acid offrom about 15:1 to about 1:1 (stoichiometric), and more preferably fromabout 4:1 to about 2:1; however, the process can operate over a muchwider range of alcohol to fatty acid ratios, with nonreacted materialssubjected to recycling or other processing steps. Generally, lowerrelative levels of alcohol to fatty acid result in decreased yield andhigher relative levels of alcohol levels to fatty acid result inincreased capital and operating expense. Some instances of operation atratios of alcohol to fatty acid over a wider range include when firststarting up the process or shutting down the process, when balancing thethroughput of the reactor to other processing steps or other processingfacilities, such as one that produces alcohol or utilizes a side stream,or when process upsets occur. When a molar ratio of 2:1 methanol tofatty acid is employed and a sodium hydroxide concentration of about 0.5wt % of the total reaction mixture is employed, the ratio of sodiumhydroxide to methanol is about 2 wt % entering the reactor and about 4wt % at the exit because about half of the alcohol is consumed in theesterification reaction.

Similarly, higher amounts of catalyst generally result in fasterreactions. However, higher amounts of catalyst can lead to higherdownstream separation costs and a different profile of side reactionproducts. The amount of homogeneous catalyst is preferably from about0.2 wt % to about 1.0 wt % of the reaction mixture when the catalyst issodium hydroxide; at typical concentration of 0.5 wt % when a 2:1 molarratio of methanol to fatty acid is used; however, in certain embodimentshigher or lower amounts can be employed. The amount of catalyst employedcan also vary depending upon the nature of the catalyst, feed materials,operating conditions, and other factors. Specifically, the temperature,pressure, free fatty acid content of the feed, and degree of mixing canchange the amount of catalyst preferably employed. While specificcatalyst amounts are discussed herein with reference to certainembodiments and examples, the preferred embodiments are not limited tosuch specific catalyst amounts. Other suitable catalyst amounts can alsobe employed in the preferred embodiments.

The esterification reaction can be performed batchwise, such as in astirred tank, or it can be performed continuously, such as in acontinuous stirred tank reactor (CSTR) or a plug flow reactor (PFR).When operated in continuous mode, a series of continuous reactors(including CSTRs, PFRs, or combinations thereof) can advantageouslyoperate in series. Alternatively, batch reactors can be arranged inparallel and/or series.

When the reactor is operated in a continuous fashion, one or more of thefeed materials is preferably metered into the process. Varioustechniques for metering can be employed (e.g., metering pumps, positivedisplacement pumps, control valves, flow meters, and the like). Whilespecific types of reactors are discussed herein with reference tocertain embodiments and examples, the preferred embodiments are notlimited to such specific reactors. Other suitable types of reactors canalso be employed in the preferred embodiments.

Fatty Acids and Fatty Acid Esters

Fatty acids are carboxylic acids with a saturated or unsaturatedaliphatic tails that are found naturally in many different fats andoils. Any unsaturated fatty acid can be suitably employed in the processof this invention, provided that the unsaturated fatty acid can bemetathesized in the manner disclosed herein. An unsaturated fatty acidcomprises a long carbon chain containing at least one carbon-carbondouble bond and terminating in a carboxylic acid group. Typically, theunsaturated fatty acid will contain greater than about 8 carbon atoms,preferably, greater than about 10 carbon atoms, and more preferably,greater than about 12 carbon atoms. Typically, the unsaturated fattyacid will contain less than about 50 carbon atoms, preferably, less thanabout 35 carbon atoms, and more preferably, less than about 25 carbonatoms. At least one carbon-carbon double bond is present along thecarbon chain, this double bond usually occurring about the middle of thechain, but not necessarily. The carbon-carbon double bond may also occurat any other internal location along the chain. A terminal carbon-carbondouble bond, at the opposite end of the carbon chain relative to theterminal carboxylic acid group, is also suitably employed, althoughterminal carbon-carbon double bonds occur less commonly in fatty acids.Unsaturated fatty acids containing the terminal carboxylic acidfunctionality and two or more carbon-carbon double bonds may also besuitably employed in the process of this invention. Since metathesis canoccur at any of the carbon-carbon double bonds, a fatty acid having morethan one double bond may produce a variety of metathesis products. Theunsaturated fatty acid may be straight or branched and substituted alongthe fatty acid chain with one or more substituents, provided that theone or more substituents are substantially inert with respect to themetathesis process. Non-limiting examples of suitable substituentsinclude alkyl moieties, preferably C₁₋₁₀ alkyl moieties, including, forexample, methyl, ethyl, propyl, butyl, and the like; cycloalkylmoieties, preferably, C₄₋₈ cycloalkyl moieties, including for example,cyclopentyl and cyclohexyl; monocyclic aromatic moieties, preferably, C₆aromatic moieties, that is, phenyl; arylalkyl moieties, preferably,C₇₋₁₆ arylalkyl moieties, including, for example, benzyl; and alkylarylmoieties, preferably, C₇₋₁₆ alkylaryl moieties, including, for example,tolyl, ethylphenyl, xylyl, and the like; as well as hydroxyl, ether,keto, aldehyde, and halide, preferably, chloro and bromo,functionalities.

Non-limiting examples of suitable unsaturated fatty acids include3-hexenoic (hydrosorbic), trans-2-heptenoic, 2-octenoic, 2-nonenoic,cis- and trans-4-decenoic, 9-decenoic (caproleic), 10-undecenoic(undecylenic), trans-3-dodecenoic (linderic), tridecenoic,cis-9-tetradeceonic (myristoleic), pentadecenoic, cis-9-hexadecenoic(cis-9-palmitoelic), trans-9-hexadecenoic (trans-9-palmitoleic),9-heptadecenoic, cis-6-octadecenoic (petroselinic), trans-6-octadecenoic(petroselaidic), cis-9-octadecenoic (oleic), trans-9-octadecenoic(elaidic), cis-11-octadecenoic, trans-11-octadecenoic (vaccenic),cis-5-eicosenoic, cis-9-eicosenoic (godoleic), cis-1′-docosenoic(cetoleic), cis-13-docosenoic (erucic), trans-13-docosenoic (brassidic),cis-15-tetracosenoic (selacholeic), cis-17-hexacosenoic (ximenic), andcis-21-triacontenoic (lumequeic) acids, as well as 2,4-hexadienoic(sorbic), cis-9-cis-12-octadecadienoic (linoleic),cis-9-cis-12-cis-15-octadecatrienoic (linolenic), eleostearic,12-hydroxy-cis-9-octadecenoic (ricinoleic), and like acids. Oleic acidis most preferred. Unsaturated fatty acids can be obtained commerciallyor synthesized by saponifying fatty acid esters, this method being knownto those skilled in the art.

Fatty acid esters are formed by condensation of a fatty acid and analcohol. Fatty acid alkyl esters are fatty acids where the hydrogen ofthe —OH of the acid group is replaced by a hydrocarbyl group, typicallya C₁ to C₃₀ alkyl group, preferably a C₁ to C₂₀ alkyl.

Fatty acid alkyl esters are fatty acids where the hydrogen of the —OH ofthe acid group is replaced by an alkyl group. Fatty acid alkyl estersuseful herein are typically represented by the formula: R̂—C(O)—O—R*,where R̂ is a C₁ to C₁₀₀ hydrocarbyl group, preferably a C₆ to C₂₂ group,preferably a C₆ to C₁₄ 1-alkene group, and R* is an alkyl group,preferably a C₁ to C₂₀ alkyl group, preferably methyl, ethyl, butyl,pentyl and hexyl. Preferred fatty acid alkyl esters useful herein aretypically represented by the formula: R̂—CH₂═CH₂—R̂—C(O)—O—R*, where eachR̂ is, independently a C₁ to C₁₀₀ alkyl group, preferably a C₆ to C₂₀,preferably a C₈ to C₁₄ alkyl group, preferably a C₉ group and R* is analkyl group, preferably a C₁ to C₂₀ alkyl group, preferably methyl,ethyl, butyl, pentyl and hexyl. Particularly preferred fatty acid alkylesters useful herein are represented by the formula:

CH₃—(CH₂)n—C═C—(CH₂)m-C(O)—O—R*,

where and R* is an alkyl group, preferably a C₁ to C₂₀ alkyl group,preferably methyl, ethyl, butyl pentyl and hexyl, m and n are,independently 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, or 16,preferably 5, 7, 9, or 11, preferably 7.

Fatty acid methyl esters are fatty acids where the hydrogen of the —OHof the acid group is replaced by methyl group. Fatty acid methyl estersuseful herein are typically represented by the formula: R̂—C(O)—O—CH₃,where R̂ is a C₁ to C₁₀₀ hydrocarbyl group, preferably a C₆ to C₂₂ group,preferably a C₆ to C₁₄-alkene group. Preferred fatty acid methyl estersuseful herein are typically represented by the formula:R̂—CH₂═CH₂—R̂—C(O)—O—CH₃, where each R̂ is, independently a C₁ to C₁₀₀alkyl group, preferably a C₆ to C₂₀, preferably a C₈ to C₁₄ alkyl group,preferably a C₉ group. Particularly preferred fatty acid methyl estersuseful herein are represented by the formula:CH₃—(CH₂)n—C═C—(CH₂)m-C(O)—O CH₃, where m and n are, independently 1, 2,3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, or 16, preferably 5, 7, 9,or 11, preferably 7.

Preferred fatty acid methyl esters include methyl palmitoleate, methyloleate, methyl gadoleate, methyl erucate, methyl linoleate, methyllinolenate, methyl soyate, and mixtures of methyl esters derived fromsoybean oil, beef tallow, tall oil, animal fats, waste oils/greases,rapeseed oil, algae oil, Canola oil, palm oil, Jathropa oil, high-oleicsoybean oil (e.g., 75 mole % or more, preferably 85 mole % or more,preferably 90 mole % or more), high-oleic safflower oil (e.g., 75 mole %or more, preferably 85 mole % or more, preferably 90 mole % or more),high-oleic sunflower oil (e.g., 75 mole % or more, preferably 85 mole %or more, preferably 90 mole % or more), and other plant or animalderived sources containing fatty acids.

A preferred source of fatty acid methyl esters for use herein includesTAG's and biodiesel sources. As described above, biodiesel refers to atransesterified vegetable oil or animal fat based diesel fuel containinglong-chain alkyl (typically methyl, propyl, or ethyl) esters. Biodieselis typically made by chemically reacting lipids (such as vegetable oil)with an alcohol. Biodiesel, TAG's and derivatives thereof may be used inthe processes described herein. Likewise, preferred fatty acid methylesters useful herein may be obtained by reacting canola oil, corn oil,soybean oil, beef tallow, tall oil, animal fats, waste oils/greases,rapeseed oil, algae oil, Canola oil, palm oil, Jathropa oil, high-oleicsoybean oil, high-oleic safflower oil, high-oleic sunflower oil ormixtures of animal and/or vegetable fats and oils with one or morealcohols (as described above), preferably methanol.

Vegetable oils useful herein preferably contain at least one site ofunsaturation and include, but are not limited to, canola, soybean, palm,peanut, mustard, sunflower, tung, tall, perilla, grapeseed, rapeseed,linseed, safflower, pumpkin corn and other oils extracted from plantseeds.

For purposes of this invention and the claims thereto the term “seedoil” refers to one or more vegetable or animal oils, such as canola oil,corn oil, soybean oil, beef tallow, tall oil, animal fats, wasteoils/greases, rapeseed oil, algae oil, peanut oil, mustard oil,sunflower oil, tung oil, perilla oil, grapeseed oil, linseed oil,safflower oil, pumpkin oil, palm oil, Jathropa oil, high-oleic soybeanoil, high-oleic safflower oil, high-oleic sunflower oil, mixtures ofanimal and/or vegetable fats and oils, castor bean oil, dehydratedcastor bean oil, cucumber oil, poppyseed oil, flaxseed oil, lesquerellaoil, walnut oil, cottonseed oil, meadowfoam, tuna oil, and sesame oils.

In a preferred embodiment, a combination of oils is used herein.Preferred combinations include two (three or four) or more of tall oil,palm oil, tallow, waste grease, rapeseed oil, canola oil, soy oil andalgae oil. Alternate useful combinations include two (three or four) ormore of soy oil, canola oil, rapeseed oil, algae oil, and tallow.

In certain embodiments processed oils, such as blown oils, are thesource of fatty acids useful herein. While vegetable oils are preferredsources of fatty acids for practicing disclosed embodiments of thepresent process, fatty acids also are available from animal fatsincluding, without limitation, lard and fish oils, such as sardine oiland herring oil, and the like. As noted above, in certain embodiments adesired fatty acid or fatty acid precursor is produced by a plant oranimal found in nature. However, particular fatty acids or fatty acidprecursors are advantageously available from genetically modifiedorganisms, such as a genetically modified plants, particularlygenetically modified algae. Such genetically modified organisms aredesigned to produce a desired fatty acid or fatty acid precursorbiosynthetically or to produce increased amounts of such compounds.

Alkyl oleates and alkyl erucates are fatty acid esters that are oftenmajor components in biodiesel produced by the transesterification ofalcohol and vegetable oils. (preferably the alkyls are a C₁ to C₃₀ alkylgroup, alternately a C₁ to C₂₀ alkyl group.) Biodiesel compositions thatare particularly useful in this invention are those which have highconcentrations of alkyl oleate and alkyl erucate esters. These fattyacid esters preferably have one site of unsaturation such thatcross-metathesis with ethylene yields 1-decene as the coproduct.Biodiesel compositions that are particularly useful are those producedfrom vegetable oils such as canola, rapeseed oil, palm oil, and otherhigh oleate oil, high erucate oils. Particularly preferred vegetableoils include those having at least 50% (on a molar basis) combined oleicand erucic fatty acid chains of all fatty acid chains, preferably 60%,preferably 70%, preferably 80%, preferably 90%.

In another embodiment, useful fatty acid ester containing mixturesinclude those having at least 50% (on a molar basis) alkyl oleate fattyacid esters, preferably 60% of alkyl oleate fatty acid esters,preferably 70% of alkyl oleate fatty acid esters, preferably 80% ofalkyl oleate fatty acid esters, preferably 90% of alkyl oleate fattyacid esters.

In another embodiment, useful fatty acid ester containing mixturesinclude those having at least 50% (on a molar basis) alkyl erucate fattyacid esters, preferably 60% of alkyl erucate fatty acid esters,preferably 70% of alkyl erucate fatty acid esters, preferably 80% ofalkyl erucate fatty acid esters, preferably 90% of alkyl erucate fattyacid esters.

In another embodiment, useful fatty acid ester containing mixturesinclude those having at least 50% (on a molar basis) combined oleic anderucic fatty acid esters of all fatty acid ester chains, preferably 60%,preferably 70%, preferably 80%, preferably 90%.

Isomerization

In another embodiment, the feed material is first isomerized, thencombined with a metathesis catalyst as described herein. For example,the processes disclosed herein may comprise providing a feed material(typically a fatty acid or fatty acid derivative), isomerizing a site ofunsaturation in the feed material (typically a fatty acid or fatty acidderivative) to produce an isomerized feed material (typically a fattyacid or fatty acid derivative), and then contacting the isomerizedmaterial with an alkene in the presence of a metathesis catalyst. Theisomerized material can be produced by isomerization with or withoutsubsequent esterification or transesterification. Isomerization can becatalyzed by known biochemical or chemical techniques. For example, anisomerase enzyme, such as a linoleate isomerase, can be used toisomerize linoleic acid from the cis 9, c is 12 isomer to the cis 9,bans 11 isomer. This isomerization process is stereospecific, however,nonstereospecific processes can be used because both cis and transisomers are suitable for metathesis. For example, an alternative processemploys a chemical isomerization catalyst, such as an acidic or basiccatalyst, can be used to isomerize an unsaturated feed material(typically a fatty acid or fatty acid derivative) having a site ofunsaturation at one location in the molecule into an isomerized, feedmaterial (typically a fatty acid or fatty acid derivative) having a siteof unsaturation at a different location in the molecule. Metal ororganometallic catalysts also can be used to isomerize an unsaturatedfeed material (typically a fatty acid or fatty acid derivative). Forexample, nickel catalysts are known to catalyze positional isomerizationof unsaturated sites in fatty acid derivatives. Similarly,esterification, transesterification, reduction, oxidation and/or othermodifications of the starting compound or products, such as a fatty acidor fatty acid derivative, can be catalyzed by biochemical or chemicaltechniques. For example, a fatty acid or fatty acid derivative can bemodified by a lipase, esterase, reductase or other enzyme before orafter isomerization. In another embodiment the isomerization describedabove may be practiced with any triacylglycerides, biodiesel, fattyacids, fatty acid esters and/or fatty acid alkyl esters describedherein, typically before contacting with the metathesis catalyst.

Metathesis Catalysts

In a preferred embodiment, the metathesis catalyst is represented by theformula:

where:M is a Group 8 metal, preferably Ru or Os, preferably Ru;X and X¹ are, independently, any anionic ligand, preferably a halogen(preferably C₁), an alkoxide or an alkyl sulfonate, or X and X¹ may bejoined to form a dianionic group and may form single ring of up to 30non-hydrogen atoms or a multinuclear ring system of up to 30non-hydrogen atoms;L is N, O, P, or S, preferably N or O;R is hydrogen or a C₁ to C₃₀ hydrocarbyl or substituted hydrocarbyl,preferably methyl; R¹, R², R³, R⁴, R⁵, R⁶, R⁷, and R⁸ are,independently, hydrogen or a C₁ to C₃₀ hydrocarbyl or substitutedhydrocarbyl, preferably methyl, ethyl, propyl or butyl, preferably R¹,R², R³, and Ware methyl;each R⁹ and R¹³ are, independently, hydrogen or a C₁ to C₃₀ hydrocarbylor substituted hydrocarbyl, preferably a C₂ to C₆ hydrocarbyl,preferably ethyl;R¹⁰, R¹¹, R¹² are, independently hydrogen or a C₁ to C₃₀ hydrocarbyl orsubstituted hydrocarbyl, preferably hydrogen or methyl;each G, is, independently, hydrogen, halogen or C₁ to C₃₀ substituted orunsubstituted hydrocarbyl (preferably a C₁ to C₃₀ substituted orunsubstituted alkyl or a substituted or unsubstituted C₄ to C₃₀ aryl);where any two adjacent R groups may form a single ring of up to 8non-hydrogen atoms or a multinuclear ring system of up to 30non-hydrogen atoms.

Preferably any two adjacent R groups may form a fused ring having from 5to 8 non hydrogen atoms. Preferably the non-hydrogen atoms are C and orO. Preferably the adjacent R groups form fused rings of 5 to 6 ringatoms, preferably 5 to 6 carbon atoms. By adjacent is meant any two Rgroups located next to each other, for example R³ and R⁴ can form a ringand/or R¹¹ and R¹² can form a ring.

In a preferred embodiment, at least one of R⁹ and R¹³ is a C₁ to C₃₀hydrocarbyl or substituted hydrocarbyl, preferably both are C₁ to C₃₀hydrocarbyl or substituted hydrocarbyl.

For purposes of this invention and claims thereto a substitutedhydrocarbyl is a radical made of carbon and hydrogen where at least onehydrogen is replaced by a heteroatom. For purposes of this invention andclaims thereto a substituted alkyl or aryl group is a radical made ofcarbon and hydrogen where at least one hydrogen is replaced by aheteroatom or a linear, branched, or cyclic substituted or unsubstitutedhydrocarbyl group having 1 to 30 carbon atoms.

Preferred alkoxides include those where the alkyl group is a phenol,substituted phenol (where the phenol may be substituted with up to 1, 2,3, 4 or 5 C₁ to C₁₋₂ hydrocarbyl groups) or a C₁ to C₁₀ hydrocarbyl,preferably a C₁ to C₁₀ alkyl group, preferably methyl, ethyl, propyl,butyl, or phenyl.

Preferred alkyl sulfonates are represented by the Formula (II):

where R² is a C₁ to C₃₀ hydrocarbyl group, fluoro-substituted carbylgroup, chloro-substituted carbyl group, aryl group, or substituted arylgroup, preferably a C₁ to C₁₂ alkyl or aryl group, preferablytrifluoromethyl, methyl, phenyl, para-methyl-phenyl.

Preferred metathesis catalysts include:2-(2,6-diethylphenyl)-3,5,5,5-tetramethylpyrrolidine[2-(i-propoxy)-5-(N,N-dimethylaminosulfonyl)phenyl]methyleneruthenium dichloride;2-(mesityl)-3,3,5,5-tetramethylpyrrolidine[2-(i-propoxy)-5-(N,N-dimethylaminosulfonyl)phenyl]methyleneruthenium dichloride;2-(2-isopropyl)-3,3,5,5-tetramethylpyrrolidine[2-(i-propoxy)-5-(N,N-dimethylaminosulfonyl)phenyl]methyleneruthenium dichloride;2-(2,6-diethyl-4-fluorophenyl)-3,3,5,5-tetramethylpyrrolidine[2-(i-propoxy)-5-(N,N-dimethylaminosulfonyl)phenyl]methyleneruthenium dichloride, and mixtures thereof.

The catalyst compounds described herein may be synthesized as follows.

The cyclic (alkyl)(amino)carbene precursor, as the aldiminium salt, canbe synthesized as reported in the literature (Angew Chem. Int. Ed. 2005,44, 5705-5709 or in WO 2006/138166). For example 2,6-diethylaniline isreacted with isobutyraldehyde in the presence of 3 angstrom molecularsieves and a catalytic amount of p-toluenesulfonic acid monohydrate at50° C. in benzene. The resulting imine is reacted with a deprotonatingagent such as lithium diisopropyl amide which is reacted with1,2-epoxy-2-methylpropane. Treatment with trifluoromethane sulfonicanhydride yields the aldiminium salt. The aldiminium salt upondeprotonation with the appropriate base such as potassiumbistrimethylsilyl amide generates the carbene at low temperatures suchas −80° C. This carbene can be reacted with ruthenium alkylidenecomplexes such as2-(i-propoxy)-5-(N,N-dimethylaminosulfonyl)phenyl]methylene}(tricyclohexylphosphine)ruthenium dichloride to generate the cyclic alky amino carbene rutheniumcomplex,2-(2,6-diethylphenyl)-3,3,5,5-tetramethylpyrrolidine[2-(i-propoxy)-5-(N,N-dimethylaminosulfonyl)phenyl]methyleneruthenium dichloride.

The resulting ruthenium alkylidene complex is an efficient catalyst orcatalyst precursor towards for the cometathesis of ethylene and methyloleate, a component of biodiesel, to generate with good selectivity1-decene and methyl-9-decenoate. The co-metathesis reaction is performedin a suitable solvent such as dichloromethane, toluene, hexane, or otheranalogous solvents. The reaction is performed at 40 to 50° C., and maybe performed at a temperature range of 0° C. to 100° C. The ethylenepressure in the reaction vessel is typically in a range of 100 to 200psi. It may be in a range of 10 psi to 1000 psi of ethylene.

Alpha-Olefin Products of the Metathesis Reaction.

In a preferred embodiment, the processes described herein produce alinear alpha olefin. The alpha-olefin, preferably linear alpha-olefin,produced herein contains at least one more carbon than the alkene usedin the reaction to make the alpha-olefin.

In another embodiment, the processes described herein produce a blend ofan alpha olefin and an ester-functionalized alpha olefin. Generally amixture of non-ester-containing alpha olefins will be produced due tothe presence of mono-, di-, and tri-unsubstituted fatty acid chains. Themajor alpha olefin products are expected to be 1-decene, 1-heptene, and1-butene. The major ester-containing alpha olefin product is methyldec-9-enoate.

In a preferred embodiment, the alpha olefin produced herein is 1-decene.Typically the 1-decene is produced with an ester.

In a preferred embodiment, the major alpha olefin produced herein is1-decene. Typically the 1-decene is produced with an ester.

In a preferred embodiment, ethylene and methyl oleate are combined withthe metathesis catalysts described herein (such as2-(2,6-diethylphenyl)-3,3,5,5-tetramethylpyrrolidine[2-(i-propoxy)-5-(N,N-dimethylaminosulfonyl)phenyl]methyleneruthenium dichloride) to produce 1-decene and methyl dec-9-enoate.

Separation of the 1-olefin (such as the 1-decene) from the ester may beby means typically known in the art such as distillation or filtration.

The linear alpha-olefin (such as 1-decene or a mixture of C₈, C₁₀, C₁₂linear alpha olefins) is then separated from any esters present andpreferably used to make poly-alpha-olefins(PAOs). Specifically, PAOs maybe produced by the polymerization of olefin feed in the presence of acatalyst such as AlCl₃, BF₃, or BF₃ complexes. Processes for theproduction of PAOs are disclosed, for example, in the following patents:U.S. Pat. Nos. 3,149,178; 3,382,291; 3,742,082; 3,769,363; 3,780,128;4,172,855 and 4,956,122, which are fully incorporated by reference. PAOsare also discussed in: Will, J. G. Lubrication Fundamentals, MarcelDekker New York, 1980. Certain high viscosity index PAO's may also beconveniently made by the polymerization of an alpha-olefin in thepresence of a polymerization catalyst such as Friedel-Crafts catalysts.These include, for example, aluminum trichloride, boron trifluoride,aluminum trichloride or boron trifluoride promoted with water, withalcohols such as ethanol, propanol, or butanol, with carboxylic acids,or with esters such as ethyl acetate or ethyl propionate or ether suchas diethyl ether, diisopropyl ether, etc., see for example, the methodsdisclosed by U.S. Pat. Nos. 4,149,178; 3,382,291; 3,742,082; 3,769,363(Brennan); 3,876,720; 4,239,930; 4,367,352; 4,413,156; 4,434,408;4,910,355; 4,956,122; 5,068,487; 4,827,073; 4,827,064; 4,967,032;4,926,004; and 4,914,254. PAO's can also be made using variousmetallocene catalyst systems. Examples include U.S. Pat. No. 6,706,828;WO 96/23751; EP 0 613 873; U.S. Pat. No. 5,688,887; U.S. Pat. No.6,043,401; WO 03/020856; U.S. Pat. No. 6,548,724; U.S. Pat. No.5,087,788; U.S. Pat. No. 6,414,090; U.S. Pat. No. 6,414,091; U.S. Pat.No. 4,704,491; U.S. Pat. No. 6,133,209; and U.S. Pat. No. 6,713,438.

PAOs are often used as additives and base stocks for lubricants, amongother things. Additional information on the use of PAO's in theformulations of full synthetic, semi-synthetic or part syntheticlubricant or functional fluids can be found in “Synthetic Lubricants andHigh-Performance Functional Fluids”, 2nd Ed. L. Rudnick, etc. MarcelDekker, Inc., N.Y. (1999). Additional information on additives used inproduct formulation can be found in “Lubricants and Lubrications, Ed. ByT. Mang and W. Dresel, by Wiley-VCH GmbH, Weinheim 2001.

In another embodiment this invention relates to:

1. A metathesis catalyst compound represented by the formula:

where:M is a Group 8 metal;X and X¹ are, independently, any anionic ligand, or X and X¹ may bejoined to form a dianionic group and may form single ring of up to 30non-hydrogen atoms or a multinuclear ring system of up to 30non-hydrogen atoms;

L is N, O P, or S;

R is hydrogen or a C₁ to C₃₀ hydrocarbyl or substituted hydrocarbyl;R¹, R², R³, R⁴, R⁵, R⁶, R⁷, and R⁸ are, independently, hydrogen or a C₁to C₃₀ hydrocarbyl or substituted hydrocarbyl;each R⁹ and R¹³ are, independently, hydrogen, a C₁ to C₃₀ hydrocarbyl orsubstituted hydrocarbyl;R¹⁰, R¹¹, R¹² are, independently, hydrogen or a C₁ to C₃₀ hydrocarbyl orsubstituted hydrocarbyl;each G, is, independently, hydrogen, halogen or C₁ to C₃₀ substituted orunsubstituted hydrocarbyl;where any two adjacent R groups may form a single ring of up to 8non-hydrogen atoms or a multinuclear ring system of up to 30non-hydrogen atoms.2. The catalyst compound of paragraph 1, wherein M is ruthenium.3. The catalyst compound of paragraph 1 or 2, wherein X and X¹ are,independently, a halogen, an alkoxide or an alkyl sulfonate.4. The catalyst compound of any of paragraphs 1 to 3, wherein X and X¹are Cl.5. The catalyst compound of any of paragraphs 1 to 4, wherein L is N orO.6. The catalyst compound of any of paragraphs 1 to 5, wherein R is a C₁to C₃₀ hydrocarbyl.7. The catalyst compound of any of paragraphs 1 to 6, wherein R ismethyl.8. The catalyst compound of any of paragraphs 1 to 7, wherein each G isindependently, a C₁ to C₃₀ substituted or unsubstituted alkyl, or asubstituted or unsubstituted C₄ to C₃₀ aryl.9. The catalyst compound of any of paragraphs 1 to 8, wherein L is N.10. The catalyst compound of paragraph 1, wherein the metathesiscatalyst compound comprises one or more of:2-(2,6-diethylphenyl)-3,5,5,5-tetramethylpyrrolidine[2-(i-propoxy)-5-(N,N-dimethylaminosulfonyl)phenyl]methyleneruthenium dichloride;2-(mesityl)-3,3,5,5-tetramethylpyrrolidine[2-(i-propoxy)-5-(N,N-dimethylaminosulfonyl)phenyl]methyleneruthenium dichloride;2-(2-isopropyl)-3,3,5,5-tetramethylpyrrolidine[2-(i-propoxy)-5-(N,N-dimethylaminosulfonyl)phenyl]methyleneruthenium dichloride;2-(2,6-diethyl-4-fluorophenyl)-3,3,5,5-tetramethylpyrrolidine[2-(i-propoxy)-5-(N,N-dimethylaminosulfonyl)phenyl]methyleneruthenium dichloride, or mixtures thereof11. A process to produce alpha-olefin comprising contacting a seed oilwith the catalyst compound of any of paragraphs 1 to 10.12. The process of paragraph 11, wherein the seed oil is selected fromthe group consisting of canola oil, corn oil, soybean oil, rapeseed oil,algae oil, peanut oil, mustard oil, sunflower oil, tung oil, perillaoil, grapeseed oil, linseed oil, safflower oil, pumpkin oil, palm oil,Jathropa oil, high-oleic soybean oil, high-oleic safflower oil,high-oleic sunflower oil, mixtures of animal and vegetable fats andoils, castor bean oil, dehydrated castor bean oil, cucumber oil,poppyseed oil, flaxseed oil, lesquerella oil, walnut oil, cottonseedoil, meadowfoam, tuna oil, sesame oils and mixtures thereof.13. The process of paragraph 11, wherein the seed oil is selected fromthe group consisting of palm oil and algae oil.14. A process to produce alpha-olefin comprising contacting atriacylglyceride with an alkene and the catalyst compound of any ofparagraphs 1 to 10, preferably wherein the alpha olefin produced has atleast one more carbon atom than the alkene.15. The process of paragraph 14, wherein the triacylglyceride iscontacted with alcohol and converted to an fatty acid ester or fattyacid alkyl ester prior to contacting with the catalyst compound of anyof paragraphs 1 to 10.16. The process of paragraph 14, wherein the triacylglyceride iscontacted with water or an alkaline reagent and converted to a fattyacid prior to contacting with the catalyst compound of any of paragraphs1 to 10.17. A process to produce alpha-olefin comprising contacting anunsaturated fatty acid with an alkene and the catalyst compound of anyof paragraphs 1 to 10, preferably wherein the alpha olefin produced hasat least one more carbon atom than the alkene.18. A process to produce alpha-olefin comprising contacting atriacylglyceride with the catalyst compound of any of paragraphs 1 to10, preferably wherein the alpha olefin produced has at least one morecarbon atom than the alkene.19. A process to produce alpha-olefin comprising contacting anunsaturated fatty acid ester and or unsaturated fatty acid alkyl esterwith an alkene and the catalyst compound of any of paragraphs 1 to 10,preferably wherein the alpha olefin produced has at least one morecarbon atom than the alkene.

20. The process of any of paragraphs 11 to 19, wherein the alpha olefinis a linear alpha-olefin having 4 to 24 carbon atoms.

21. The process of any of paragraphs 11 to 20, wherein the alkene isethylene, propylene, butene, hexene or octene.

22. The process of any of paragraphs 19 to 21, wherein the fatty acidester is a fatty acid methyl ester.

23. The process of any of paragraphs 14 to 22, wherein thetriacylglyceride, fatty acid, fatty acid alkyl ester, fatty acid esteris derived from biodiesel.

24. The process of any of paragraphs 11 to 23, wherein the alpha-olefinis butene-1, decene-1 and or heptene-1.25. The process of any of paragraphs 11 to 24, wherein the productivityof the process is at least 200 g of linear alpha-olefin per mmol ofcatalyst per hour.26. The process of any of paragraphs 11 to 25, wherein the selectivityof the process is at least 20 wt % linear alpha-olefin, based upon theweight to the material exiting the reactor.27. The process of any of paragraphs 11 to 26, wherein the turnovernumber, defined as the moles of alpha olefin formed per mol of catalyst,of the process is at least 10,000.28. The process of any of paragraphs 11 to 27, wherein the yield, whenconverting unsaturated fatty acids, unsaturated fatty acid esters,unsaturated fatty acid alkyl esters or mixtures thereof, is 30% or more,said yield being defined as defined as the moles of alpha olefin formedper mol of unsaturated fatty acids, unsaturated fatty acid esters,unsaturated fatty acid alkyl esters or mixtures thereof introduced intothe reactor.29. The process of any of paragraphs 11 to 27, wherein the yield, whenconverting TAGs as represented in the formula below, is 30% or more,said yield being defined as defined as the moles of alpha olefin formeddivided by (the moles of unsaturated R^(a)+moles of unsaturatedR^(b)+moles of unsaturated R^(c)) introduced into the reactor,

where R^(a), R^(b) and R^(c) each, independently, represent a saturatedor unsaturated hydrocarbon chain.30. The process of paragraph 28, wherein the yield is 60% or more.31. A process to produce C₄ to C₂₄ linear alpha-olefin comprisingcontacting a feed material with an alkene selected from the groupconsisting of ethylene, propylene butene, pentene, hexene, heptene,octene, nonene and mixtures thereof and a metathesis catalyst compoundof any of paragraphs 1 to 10, wherein the feed material is atriacylglyceride, fatty acid, fatty acid alkyl ester, and/or fatty acidester derived from seed oil.32. The process of paragraph 31, wherein the alkene is ethylene, thealpha olefin is 1-butene, 1-heptene and or -decene, and the feedmaterial is a fatty acid methyl ester, and/or fatty acid ester.

EXPERIMENTAL SECTION Tests and Materials

All molecular weights are number average unless otherwise noted. Allmolecular weights are reported in g/mol unless otherwise noted.

THF is tetrahydrofuran.

Products were analyzed by gas chromatography (Agilent 6890N withauto-injector) using helium as a carrier gas at 38 cm/sec. A columnhaving a length of 60 m(J & W Scientific DB-1, 60 m×0.25 mm I.D.×1.0 μmfilm thickness) packed with a flame ionization detector (FID), anInjector temperature of 250° C., and a Detector temperature of 250° C.were used. The sample injected into the column in an oven at 70° C.,then heated to 275° C. over 22 minutes (ramp rate 10° C./min to 100° C.,30° C./min to 275° C., hold).

Examples Synthesis Example 1

Synthesis of (E)-2,6-diethyl-N-(2-methylpropylidene)aniline (compound1). Benzene (150 mL) was added to 2,6-diethylaniline (18.59 g, 124.6mmol) and 3 angstrom molecular sieves (ca. 50 mL). Then isobutyraldehyde(9.43 g, 131 mmol) and p-toluenesulfonic acid monohydrate (20 mg, 0.011mmol) were added. The flask was sealed and heated to 50° C. Afterstirring overnight the very pale yellow solution was filtered and thevolatiles were removed under reduced pressure to afford the product as aclear, pale yellow oil. Yield: 22.5 g, 84.6%. ¹H NMR (C₆D₆): δ 7.21 (1H,d), 7.02 (2H, m), 2.47 (4H, q), 2.39 (1H, m), 1.11 (6H, t), 1.01 (6H,d).

Synthesis of lithium (2,6-diethylphenyl)(2-methylprop-1-enyl)amide(compound 2). Benzene (70 mL) and compound 1 (6.63 g, 32.6 mmol) werecombined. Then solid lithium diisopropylamide (4.01 g, 37.4 mmol) wasadded. The mixture was heated to 50° C. to form a cloudy red-orangesolution. After a few hours the solution was filtered throughdiatomaceous earth to afford a clear yellow solution. The volatiles wereevaporated to give a yellow solid. Pentane (15 mL) was added and themixture was stirred briefly and then cooled to −10° C. overnight. Theproduct was then collected on a glass frit and washed with pentane (2×20mL) to give a white solid that was dried under reduced pressure. Yield:5.50 g, 80.6%.

Synthesis of1-(2,6-diethylphenyl)-2,2,4,4-tetramethyl-3,4-dihydro-2H-pyrroliumtriflate (compound 3). Et₂O (100 mL) was added to compound 2 (5.50 g,26.3 mmol) to form a clear yellow solution. An Et₂O (5 mL) solution of1,2-epoxy-2-methylpropane (1.90 g, 26.3 mmol) was added dropwise overabout 10 seconds, and the mixture was stirred overnight. The next daythe mixture was cooled to −80° C. and trifluoromethanesulfonic anhydride(7.42 g, 26.3 mmol) was added dropwise. The mixture was warmed toambient temperature over 1 hour. A thick suspension formed. Afterstirring for an additional hour, the solid was collected on a glass fritand washed with Et₂O (3×15 mL). The solid was dried under reducedpressure. This was then extracted with CH₂Cl₂ (60 mL) and filteredthrough diatomaceous earth. The filter cake was washed with CH₂Cl₂ (2×30mL). The combined CH₂Cl₂ extracts were evaporated to an oil and Et₂O (15mL) was added to cause a white crystalline solid to form. The solutionwas cooled to −10° C. overnight. The solid was then collected and driedunder reduced pressure to afford 1.48 g of product. To obtain additionalproduct the filter cake was loaded into a thimble. This was placed in aSoxhlet extractor and the solid was extracted with hot CH₂Cl₂ overnight.The resulting CH₂Cl₂ extract was evaporated and Et₂O (10 mL) was addedto afford additional product as off-white crystals. Total yield: 3.28 g,30.6%. ¹H NMR(C₆D₆): δ 7.21 (1H, d), 7.02 (2H, m), 2.47 (4H, q), 2.39(1H, m), 1.11 (6H, t), 1.01 (6H, d).

Synthesis of2-(2,6-diethylphenyl)-3,3,5,5-tetramethylpyrrolidine[2-(i-propoxy)-5-(N,N-dimethylaminosulfonyl)phenyl]methyleneruthenium dichloride (compound 4). Tetrahydrofuran (40 mL) was added toKN(SiMe3)₂ (0.379 g, 1.90 mmol) to form a homogeneous solution. At −80°C. solution of compound 3 (0.775 g, 1.90 mmol) and THF (10 mL) was addeddropwise over about 10 seconds. After 30 seconds a THF (10 mL) solutionof{[2-(i-propoxy)-5-(N,N-dimethyl-aminosulfonyl)phenyl]methylene}-(tricyclohexylphosphine)ruthenium dichloride (0.612 g, 0.865 mmol), which had been cooled to−10° C., was added dropwise over about 15 seconds. The mixture wasstirred for 10 minutes then warmed to ambient temperature. The mixturewas then stirred for 2 h, then the volatiles were removed under reducedpressure. The residue was extracted with 20 mL of a 3:2 mixture ofhexane:CH₂Cl₂ and filtered. This solution was loaded on to a SiO₂ column(1.25″×8″) that had been packed with the same solvent mixture. Thecolumn was eluted with 3:2 hexane:CH₂Cl₂ (300 mL) and then the solventstrength was gradually increased to pure CH₂Cl₂. The product eluted as adark green band. Removal of the volatiles afforded a dark green oil thatcrystallized upon the addition of pentane (2 mL) and cooling to −10° C.overnight. The product was isolated as green flocculent crystals thatwere dried under reduced pressure (0.038 g, 6.4%). ¹H NMR (CD₂Cl₂): δ16.26 (1H, s, RuCH—), 7.96 (1H, dd), 7.64 (1H, t), 7.47 (2H, d), 7.18(1H, d, J=2 Hz), 7.11 (1H, d), 5.22 (1H, sept), 2.64 (6H, s), 2.53 (4H,m), 2.19 (2H, s), 2.07 (6H, s), 1.77 (6H, d), 1.32 (6H, s), 0.88 (6H,t).

Cross Metathesis of Methyl Oleate with Ethylene Example 1

A stock solution was made by dissolving 4.5 mg of2-(2,6-diethylphenyl)-3,3,5,5-tetramethylpyrrolidine[2-(i-propoxy)-5-(N,N-dimethylaminosulfonyl)phenyl]methylene ruthenium dichloride in 25 mL anhydrousdichloromethane. 1.0 mL (0.87 g) methyl oleate, 1.26 g (125 nmolcatalyst) of catalyst stock solution, 3.7 g anhydrous dichloromethane,and 0.152 g (0.2 mL) tetradecane as an internal standard were weighedout and then placed in a Fisher-Porter bottle equipped with a stir bar.The vessel was then filled with ethylene to 150 psig (1034 kPa) andplaced in an oil bath heated to 40° C. for 2 hours. After completion thevessel was depressurized and approximately 0.5 mL ethyl vinyl ether wasadded to stop the reaction. A sample was then taken and analyzed by GCas described above.

Example 2

This example was run according to the procedure in Example 1, exceptthat the amount of catalyst for this run was halved such that 0.63 g(62.5 nmol catalyst) of catalyst stock solution was added along with 4.4g anhydrous dichloromethane. The amount of methyl oleate (1.0 mL, 0.876g) and tetradecane standard (0.2 mL, 0.152 g) remained the same. Thereactants were placed in a Fisher-Porter bottle and into a 40° C. oilbath for 2 hours, after which ethyl vinyl ether was added to stop thereaction. A sample was taken and analyzed by GC as described above.

Example 3

This example was run according to the procedure in Example 2, exceptthat the amount of catalyst was for this run was halved from theprevious run to 0.31 g (31.25 nmol catalyst) of catalyst stock solutionwhich was added along with 4.7 g anhydrous dichloromethane. The amountof methyl oleate and internal standard remained the same. The reactantswere placed in a Fisher-Porter bottle and into a 40° C. oil bath for 2hours, after which ethyl vinyl ether was added to stop the reaction. Asample was taken and analyzed by GC as described above.

Example 4

This example was run according to the procedure in Example 3, exceptthat the catalyst loading was halved once more to 0.157 g (15.62 nmolcatalyst) of catalyst stock solution along with 4.9 g anhydrousdichloromethane. Methyl oleate and standard amounts remained the same.The reactants were placed in a Fisher-Porter bottle and into a 40° C.oil bath for 2 hours, after which ethyl vinyl ether was added to stopthe reaction. A sample was taken and analyzed by GC as described above.

Example 5

This example was run according to the procedure in Example 4, expectthat the catalyst loading was increased to 0.235 g (23.43 nmol catalyst)of stock solution with 4.8 g anhydrous dichloromethane. Methyl oleateand standard amounts remained the same. The reactants were placed in aFisher-Porter bottle and into a 40° C. oil bath for 2 hours, after whichethyl vinyl ether was added to stop the reaction. A sample was taken andanalyzed by GC as described above.

In Table 2, % yield is shown as a percentage and defined as100×[micromoles of 1-decene]/[micromoles of methyl oleate weighed intoreactor]. 1-decene selectivity is shown as a percentage and is definedas 100×[peak area of 1-decene and methyl-9-decenoate]/[sum of peak areasof 1-decene, methyl-9-decenoate, and the homometathesis products,9-octadecene, and 1,18-dimethyl-9-octadecenedioate]. Catalyst turnoverfor production of the 1-decene is defined as the [micromoles of1-decene]/([micromoles of catalyst].

TABLE 2 Reaction conditions, 40° C., 2 hours nmoles No. TurnoversExample Catalyst % Selectivity % Yield 1-Decene 1 125 92.0 62.8 14,700 262.5 88.2 52.9 24,800 3 31.25 90.2 46.7 43,840 5 23.43 92.4 43.6 52,4004 15.62 91.0 31.7 59.400

All documents described herein are incorporated by reference herein,including any priority documents and/or testing procedures to the extentthey are not inconsistent with this text, provided however that anypriority document not named in the initially filed application or filingdocuments is NOT incorporated by reference herein. As is apparent fromthe foregoing general description and the specific embodiments, whileforms of the invention have been illustrated and described, variousmodifications can be made without departing from the spirit and scope ofthe invention. Accordingly, it is not intended that the invention belimited thereby. Likewise, the term “comprising” is consideredsynonymous with the term “including” for purposes of Australian law.

1. A metathesis catalyst compound represented by the formula:

where: M is a Group 8 metal; X and X¹ are, independently, any anionicligand, or X and X¹ may be joined to form a dianionic group and may formsingle ring of up to 30 non-hydrogen atoms or a multinuclear ring systemof up to 30 non-hydrogen atoms; L is N, O P, or S; R is hydrogen or a C₁to C₃₀ hydrocarbyl or substituted hydrocarbyl; R¹, R², R³, R⁴, R⁵, R⁶,R⁷, and R⁸ are, independently, hydrogen or a C₁ to C₃₀ hydrocarbyl orsubstituted hydrocarbyl; each R⁹ and R¹³ are, independently, hydrogen, aC₁ to C₃₀ hydrocarbyl or substituted hydrocarbyl; R¹⁰, R¹¹, R¹² are,independently, hydrogen or a C₁ to C₃₀ hydrocarbyl or substitutedhydrocarbyl; each G, is, independently, hydrogen, halogen or C₁ to C₃₀substituted or unsubstituted hydrocarbyl; and where any two adjacent Rgroups may form a single ring of up to 8 non-hydrogen atoms or amultinuclear ring system of up to 30 non-hydrogen atoms.
 2. The catalystcompound of claim 1, wherein M is ruthenium.
 3. The catalyst compound ofclaim 1, wherein X and X¹ are, independently, a halogen, an alkoxide ora alkyl sulfonate.
 4. The catalyst compound claim 1, wherein X and X¹are Cl.
 5. The catalyst compound of claim 1, wherein L is N or O.
 6. Thecatalyst compound of claim 1, wherein R is a C₁ to C₃₀ hydrocarbyl. 7.The catalyst compound of claim 1, wherein R is methyl.
 8. The catalystcompound of claim 1, wherein each G is independently, a C₁ to C₃₀substituted or unsubstituted alkyl, or a substituted or unsubstituted C₄to C₃₀ aryl.
 9. The catalyst compound of claim 2, wherein L is N. 10.The catalyst compound of claim 1, wherein the metathesis catalystcompound comprises one or more of:2-(2,6-diethylphenyl)-3,5,5,5-tetramethylpyrrolidine[2-(i-propoxy)-5-(N,N-dimethylaminosulfonyl)phenyl]methyleneruthenium dichloride;2-(mesityl)-3,3,5,5-tetramethylpyrrolidine[2-(i-propoxy)-5-(N,N-dimethylaminosulfonyl)phenyl]methyleneruthenium dichloride;2-(2-isopropyl)-3,3,5,5-tetramethylpyrrolidine[2-(i-propoxy)-5-(N,N-dimethylaminosulfonyl)phenyl]methyleneruthenium dichloride;2-(2,6-diethyl-4-fluorophenyl)-3,3,5,5-tetramethylpyrrolidine[2-(i-propoxy)-5-(N,N-dimethylaminosulfonyl)phenyl]methyleneruthenium dichloride, or mixtures thereof.
 11. A process to producealpha-olefin comprising contacting a feed oil with a metathesis catalystcompound represented by the formula:

where: M is a Group 8 metal; X and X¹ are, independently, any anionicligand, or X and X¹ may be joined to form a dianionic group and may formsingle ring of up to 30 non-hydrogen atoms or a multinuclear ring systemof up to 30 non-hydrogen atoms; L is N, O P, or S; R is hydrogen or a C₁to C₃₀ hydrocarbyl or substituted hydrocarbyl; R¹, R², R³, R⁴, R⁵, R⁶,R⁷, and R⁸ are, independently, hydrogen or a C₁ to C₃₀ hydrocarbyl orsubstituted hydrocarbyl; each R⁹ and R¹³ are, independently, hydrogen, aC₁ to C₃₀ hydrocarbyl or substituted hydrocarbyl; R¹⁰, R¹¹, R¹² are,independently, hydrogen or a C₁ to C₃₀ hydrocarbyl or substitutedhydrocarbyl; each G, is, independently, hydrogen, halogen or C₁ to C₃₀substituted or unsubstituted hydrocarbyl; and where any two adjacent Rgroups may form a single ring of up to 8 non-hydrogen atoms or amultinuclear ring system of up to 30 non-hydrogen atoms.
 12. The processof claim 11, wherein the feed oil is a seed oil is selected from thegroup consisting of canola oil, corn oil, soybean oil, rapeseed oil,algae oil, peanut oil, mustard oil, sunflower oil, tung oil, perillaoil, grapeseed oil, linseed oil, safflower oil, pumpkin oil, palm oil,Jathropa oil, high-oleic soybean oil, high-oleic safflower oil,high-oleic sunflower oil, mixtures of animal and vegetable fats andoils, castor bean oil, dehydrated castor bean oil, cucumber oil,poppyseed oil, flaxseed oil, lesquerella oil, walnut oil, cottonseedoil, meadowfoam, tuna oil, sesame oils and mixtures thereof.
 13. Theprocess of claim 11, wherein the feed oil is selected from the groupconsisting of palm oil and algae oil.
 14. A process to producealpha-olefin comprising contacting a triacylglyceride with an alkene anda metathesis catalyst compound represented by the formula:

where: M is a Group 8 metal; X and X¹ are, independently, any anionicligand, or X and X¹ may be joined to form a dianionic group and may formsingle ring of up to 30 non-hydrogen atoms or a multinuclear ring systemof up to 30 non-hydrogen atoms; L is N, O P, or S; R is hydrogen or a C₁to C₃₀ hydrocarbyl or substituted hydrocarbyl; R¹, R², R³, R⁴, R⁵, R⁶,R⁷, and R⁸ are, independently, hydrogen or a C₁ to C₃₀ hydrocarbyl orsubstituted hydrocarbyl; each R⁹ and R¹³ are, independently, hydrogen, aC₁ to C₃₀ hydrocarbyl or substituted hydrocarbyl; R¹⁰, R¹¹, R¹² are,independently, hydrogen or a C₁ to C₃₀ hydrocarbyl or substitutedhydrocarbyl; each G, is, independently, hydrogen, halogen or C₁ to C₃₀substituted or unsubstituted hydrocarbyl; where any two adjacent Rgroups may form a single ring of up to 8 non-hydrogen atoms or amultinuclear ring system of up to 30 non-hydrogen atoms; and wherein thealpha olefin produced has at least one more carbon atom than the alkene.15. The process of claim 14, wherein the triacylglyceride is contactedwith alcohol and converted to an fatty acid ester or fatty acid alkylester prior to contacting with the catalyst compound.
 16. The process ofclaim 14, wherein the triacylglyceride is contacted with water andconverted to a fatty acid prior to contacting with the catalystcompound.
 17. A process to produce alpha-olefin comprising contacting anunsaturated fatty acid with an alkene and the catalyst compound ofclaim
 1. 18. A process to produce alpha-olefin comprising contacting atriacylglyceride with the catalyst compound of claim
 1. 19. A process toproduce alpha-olefin comprising contacting an unsaturated fatty acidester and or unsaturated fatty acid alkyl ester with an alkene and thecatalyst compound of claim
 1. 20. The process claim 19, wherein thealpha olefin is a linear alpha-olefin having 4 to 24 carbon atoms. 21.The process of claim 19, wherein the alkene is ethylene, propylene,butene, hexene or octene.
 22. The process of claim 19, wherein the fattyacid alkyl ester is a fatty acid methyl ester.
 23. A process to producealpha-olefin comprising contacting a feed material with an alkene and ametathesis catalyst compound represented by the formula:

where: M is a Group 8 metal; X and X¹ are, independently, any anionicligand, or X and X¹ may be joined to form a dianionic group and may formsingle ring of up to 30 non-hydrogen atoms or a multinuclear ring systemof up to 30 non-hydrogen atoms; L is N, O P, or S; R is hydrogen or a C₁to C₃₀ hydrocarbyl or substituted hydrocarbyl; R¹, R², R³, R⁴, R⁵, R⁶,R⁷, and R⁸ are, independently, hydrogen or a C₁ to C₃₀ hydrocarbyl orsubstituted hydrocarbyl; each R⁹ and R¹³ are, independently, hydrogen, aC₁ to C₃₀ hydrocarbyl or substituted hydrocarbyl; R¹⁰, R¹¹, R¹² are,independently, hydrogen or a C₁ to C₃₀ hydrocarbyl or substitutedhydrocarbyl; each G, is, independently, hydrogen, halogen or C₁ to C₃₀substituted or unsubstituted hydrocarbyl; and where any two adjacent Rgroups may form a single ring of up to 8 non-hydrogen atoms or amultinuclear ring system of up to 30 non-hydrogen atoms, wherein thefeed material is a triacylglyceride, fatty acid, fatty acid alkyl ester,and/or fatty acid ester derived from biodiesel.
 24. The process of claim19, wherein the alpha-olefin is butene-1, decene-1 and or heptene-1. 25.The process of claim 14, wherein the productivity of the process is atleast 200 g of linear alpha-olefin per mmol of catalyst per hour. 26.The process of claim 14, wherein the selectivity of the process is atleast 20 wt % linear alpha-olefin, based upon the weight to the materialexiting the reactor.
 27. The process of claim 14, wherein the turnovernumber, defined as the moles of alpha olefin formed per mol of catalyst,of the process is at least 10,000.
 28. The process of claim 14, whereinthe yield, when converting unsaturated fatty acids, unsaturated fattyacid esters, unsaturated fatty acid alkyl esters or mixtures thereof, is30% or more, said yield being defined as defined as the moles of alphaolefin formed per mol of unsaturated fatty acids, unsaturated fatty acidesters, unsaturated fatty acid alkyl esters or mixtures thereofintroduced into the reactor.
 29. The process of claim 14, wherein theyield, when converting triacylglycerides as represented in the formulabelow, is 30% or more, said yield being defined as defined as the molesof alpha olefin formed divided by (the moles of unsaturated R^(a)+molesof unsaturated R^(b)+moles of unsaturated R^(c)) introduced into thereactor,

where R^(a), R^(b) and R^(c) each, independently, represent a saturatedor unsaturated hydrocarbon chain.
 30. The process of claim 28, whereinthe yield is 60% or more.
 31. A process to produce C₄ to C₂₄ linearalpha-olefin comprising contacting a feed material with an alkeneselected from the group consisting of ethylene, propylene butene,pentene, hexene, heptene, octene, nonene and mixtures thereof and ametathesis catalyst compound represented by the formula:

where: M is a Group 8 metal; X and X¹ are, independently, any anionicligand, or X and X¹ may be joined to form a dianionic group and may formsingle ring of up to 30 non-hydrogen atoms or a multinuclear ring systemof up to 30 non-hydrogen atoms; L is N, O P, or S; R is hydrogen or a C₁to C₃₀ hydrocarbyl or substituted hydrocarbyl; R¹, R², R³, R⁴, R⁵, R⁶,R⁷, and R⁸ are, independently, hydrogen or a C₁ to C₃₀ hydrocarbyl orsubstituted hydrocarbyl; each R⁹ and R¹³ are, independently, hydrogen, aC₁ to C₃₀ hydrocarbyl or substituted hydrocarbyl; R¹⁰, R¹¹, R¹² are,independently, hydrogen or a C₁ to C₃₀ hydrocarbyl or substitutedhydrocarbyl; each G, is, independently, hydrogen, halogen or C₁ to C₃₀substituted or unsubstituted hydrocarbyl; and where any two adjacent Rgroups may form a single ring of up to 8 non-hydrogen atoms or amultinuclear ring system of up to 30 non-hydrogen atoms, wherein thefeed material is a triacylglyceride, fatty acid, fatty acid alkyl ester,and/or fatty acid ester derived from seed oil.
 32. The process of claim31, wherein the alkene is ethylene, the alpha olefin is 1-butene,1-heptene and or 1-decene, and the feed material is a fatty acid methylester, and/or fatty acid ester.